渣油加氢脱残炭脱硫催化剂RCS-31的开发

根据渣油加氢脱残炭反应机理,通过优化载体孔结构和活性金属组分、调整浸渍工艺、改善催化剂表面性能,开发了渣油加氢脱残炭脱硫催化剂RCS-31。中型装置活性评价结果表明,与上一代渣油加氢脱残炭催化剂相比,RCS-31催化剂相对脱残炭活性提高超过10个百分点以上。工业试生产结果表明,RCS-31工业放大催化剂的活性达到实验室催化剂水平,适合于大规模工业生产和应用。     

茂名石化200万t/a S-RHT装置第10周期初期运行总结

总结茂名石化渣油加氢工业装置第10周期初期运行情况。工业应用结果表明,在原料劣质化、进料高负荷的操作条件下,两系列渣油加氢催化剂表现出良好脱硫、脱氮、脱金属及残炭加氢转化能力,能够为下游催化裂化装置提供更优质进料。     

FZC—20Q系列渣油加氢脱金属催化剂的研制及工业放大

我国第一代渣油加氢脱金属（HDM）催化剂，即FZC－20系列催化剂性能优异，已多次进行工业生产及工业应用，取得良好的应用效果，1999年底，该催化剂在茂名石化公司S－RHT渣油加氢处理装置上投入使用。     

渣油加氢催化剂孔结构对反应活性的影响

在3L中型加氢试验装置上考察了渣油加氢脱硫催化剂孔结构对反应活性的影响，试验结果表明，当孔结构发生变化时，催化剂的脱硫、脱氮、脱残炭及脱金属反应活性呈现不同的变化规律。     

S-RHT渣油加氢脱金属催化剂的研制及工业应用

本文论述了渣油加氢脱金属催化剂的基本设计思路,介绍了抚顺石油化工研究院开发的FZC-20系列渣油加氢脱金属催化剂的性能及其配套催化剂在茂名S-RHT渣油加氢处理装置上工业应用标定结果。工业应用的标定结果表明,FZC-20系列渣油加氢脱金属催化剂及其配套催化剂具有良好的活性及稳定性,装置运行平稳,产品质量好,完全能满足炼厂长期生产要求。     

铁基沸腾床渣油加氢脱硫催化剂研究

制备了具有相同活性金属质量分数的铁基和非铁基沸腾床渣油加氢脱硫催化剂.通过BET、XRD、Raman、H2-TPR、CO吸附原位红外和吡啶红外技术对催化剂进行表征,并采用模型化合物和减压渣油考察了催化剂的加氢脱硫反应机理和加氢活性.结果表明:催化剂的加氢脱硫反应按照直接脱硫反应路径进行,铁基催化剂表现出更高的渣油加氢脱硫、加氢脱残炭和加氢脱金属活性.这是由于铁的加入,增加了催化剂的红外酸量和MoS2活性物种数量,提高了活性金属的利用率,在活性金属质量分数相当的情况下,使催化剂具有更高的加氢活性.     

催化剂性能对渣油加氢处理催化剂杂质沉积分布的影响

催化剂性能会改变催化剂运转过程中杂质的沉积分布规律。通过对催化剂物化性质的调整,可有效改善催化剂上杂质的分布,提高床层金属容纳能力、减少积炭,延长装置运转周期。通过对工业运转后的渣油加氢催化剂进行分析发现,中国石油化工股份有限公司石油化工科学研究院开发的新一代高效渣油加氢处理RHT系列催化剂在物化性质方面的改善使其性能明显优于第一代RHT催化剂,具有高脱金属活性、高容金属能力和减少催化剂表面积炭的能力,有利于发挥催化剂整体优势和延长运转周期。     

PHR系列固定床渣油加氢催化剂的研制开发与工业应用

中国石油石油化工研究院通过深入研究渣油原料的结构组成与加氢转化行为特征,成功开发出包括保护剂、脱金属剂、脱硫剂和脱残炭剂4大类共12个牌号的PHR系列固定床渣油加氢催化剂。在保护剂中构建了"毫米-微米-纳米"多级孔体系,其微米级孔（PHR-402、PHR-403催化剂）与纳米级孔（PHR-404催化剂）均为双峰分布,微米级孔（PHR-402、PHR-403催化剂）主要分布在1μm附近区域和30~200μm的较宽泛区域,纳米级孔（PHR-404催化剂）的集中孔径则分别约为13nm和250nm,纳米级孔中大于100nm的孔比例达到35%。脱金属剂具有双峰分布的孔结构及内高外低的活性金属含量分布,其"扩散孔"孔径达到微米级（2300nm）,大于100nm的孔比例超过20%。工业应用结果表明,PHR系列渣油加氢催化剂具有高而稳定的脱硫、脱氮、脱残炭等活性,催化剂内部孔结构的利用率高,且床层压降更低,有利于延长装置运转周期。     

孔道结构对渣油加氢脱金属催化剂活性的影响

选择性制备3种不同孔道结构的渣油加氢脱金属催化剂,并进行渣油加氢脱金属和加氢脱硫活性评价。结果表明,一定量大孔(>50 nm)的存在,能够提高催化剂单位表面积的加氢脱金属活性;加氢脱硫活性与体积比表面积成正比。     

第三代渣油加氢催化剂在中国石油化工股份有限公司齐鲁分公司胜利炼油厂应用

中国石油化工股份有限公司石油化工科学研究院第三代RHT系列渣油加氢催化剂及应用技术在中国石油化工股份有限公司齐鲁分公司胜利炼油厂取得重大突破。经过科技人员10年的不懈努力,工业装置全系列催化剂6个周期的全面综合比较,中国石油化工股份有限公司齐鲁分公司决定在渣油加氢装置第11个运转周期,两个系列反应器全部采用中国石油化工股份有限公司石油化工科学研究院第三代渣油加氢催化剂,标志着中国石油化工股份有限公司石油化工科学研究院渣油加氢催化剂的开发与应用又向前迈进了一大步。     

粒径变化对沸腾床渣油加氢催化剂的影响

采用抚顺石油化工研究院(FRIPP)自主研发的微球形催化剂,以伊朗常压渣油(IRAR)为原料油,在间歇式高压反应釜内考察了粒径变化对沸腾床渣油加氢催化剂性能和加氢反应后催化剂性质影响.结果表明:减小催化剂粒径可以提高脱金属率、脱硫率、残炭转化率.生焦后催化剂的比表面积、孔容损失严重.     

Studies on recycling and utilization of spent catalysts: Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al₂O₃ with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst.     

Preparation of heavy oil hydrotreating catalyst from spent residue hydroprocessing catalysts

In recent years, increasing emphasis has been placed on recycling spent hydroprocessing catalysts due to environmental regulations which list them as hazardous waste materials. In the present work, the recycling of spent residue hydroprocessing catalysts that contained high levels of vanadium was investigated by using them in the preparation of active new hydrotreating catalyst after subjecting them to different treatments such as decoking, acid-leaching and hydrothermal treatment. Catalyst extrudates containing different levels of V, Mo and Ni on Al₂O₃ were prepared by mixing the spent catalyst powder with boehmite in different proportions followed by peptization, kneading and extrusion. The prepared catalyst extrudates were characterized by chemical analysis and surface area and porosity measurements. The HDS and HDM activities of the catalysts were tested using Kuwait atmospheric residue as feed and compared with that of a reference HDM catalyst. Partial leaching of vanadium from the spent catalyst opened up the pores, and the catalyst prepared by mixing the metal-leached spent catalyst (MLSC) with boehmite had higher surface area and pore volume and showed higher hydrotreating activity than that prepared from unleached spent catalyst. Hydrothermal treatment of the spent catalyst increased its porosity and surface area. Catalysts prepared from hydrothermally treated spent catalyst (HTSC) had higher surface area and pore volume and showed higher HDM and HDS activities than that prepared from the spent catalyst without hydrothermal treatment. The catalysts prepared from the treated spent catalysts also exhibited substantially higher HDM and HDS activities than the reference commercial HDM catalyst. The results indicate that spent catalysts containing high levels of vanadium together with Mo and Ni on Al₂O₃ can be used in the preparation of active HDM/HDS catalysts, and thereby, their environmental problem can be reduced.     

RN-10催化剂在柴油加氢装置的工业应用

RN-10催化剂在柴油加氢精制装置的工业应用表明，该催化剂具有反应起始温度低、稳定性好、使用空速高以及脱硫、脱氮活性高等特点，满足了对柴油产品质量的更高要求。     

Deactivation of HDS catalyst in two-stage RDS process: II. Effect of crude oil and deactivation mechanism

Aging tests of HDS catalyst in two-stage RDS process (HDM/HDS) were performed with Arabian light atmospheric residue as feedstock and the deactivation mechanism was discussed by comparison with previous results using Kuwait residue. It was found that the HDS catalyst in the second stage was deactivated by coke deposition rather than by metals and that asphaltene aromaticity in the feed was a good index for the HDS catalyst deactivation. Furthermore, it was confirmed that fouling rate was strongly affected by the combination of asphaltene aromaticity in HDS feed and reaction temperature in HDS itself.     

Effect of catalyst composition on the hydrodesulphurization and hydrodemetallization of atmospheric residual oil

A series of CoMo/Al₂O₃ catalysts containing a third additive, a Si, Ti, or P compound, were prepared using a consecutive impregnation method. The activities for the hydrodesulphurization (HDS), hydrodemetallization (HDM) and Conradson carbon residue (CCR) reduction of atmospheric residual oil were tested in a semi-batch basket type reactor. Cycle-aging tests were carried out for comparison of catalyst stability. The intrinsic rate constants of HDS from a semi-empirical calculation were used to test the coke tolerance of the catalysts. The CoMo/Al₂O₃ catalyst with a titanium compound added exhibited the highest activity enhancement for HDS and HDM reactions. It was also found that the surface activity maintenance can be effectively improved by the addition of an appropriate amount of titanium compound. The activity and stability of CoMo and NiMo catalysts for the HDS and HDM reactions were also compared.     

Activity of hydroprocessing catalysts prepared by reprocessing spent catalysts

In this study, two spent catalysts from the 3rd and 4th fixed beds of the atmospheric residue desulfurization (ARDS) process and one spent catalyst from the H-Oil process employing the expanded bed were used as the starting material for preparation of hydroprocessing catalysts. The spent catalysts were used either in a coked or decoked form. The procedures involved pulverizing the spent catalysts before mixing, kneading and extruding with boehmite in the presence of peptizing agent such as HNO₃. The hydrodesufurization (HDS) and hydrodemetallization (HDM) activities of the new catalysts were evaluated in the microreactor using the atmospheric residue derived from Kuwait crude. The new catalysts prepared from the spent catalysts used in the fixed bed reactors exhibited higher activity than that of commercial catalysts. The HDS activity of the new catalysts prepared from spent catalysts used in the ebullated bed reactor was much lower than that of the other catalysts. This was attributed to a high content of vanadium in the former spent catalyst. At the same time, the adverse effect of vanadium on HDM was much less evident.